Coating compositions for moistureproofing by hot melt coating



Patented on. 22, 1946 I 7 2,409,985

U IT STATES PATENT OFFICE COATING COI'CPOSITIONS FOR MOISTURE- PROOFING BY HOT MELT COATING 1 Martin Salo, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey t No-Drawing. Application March 18,1944,

Serial No. 527,153 8 Claims. (Cl. 260-46) 1 Y 2 y a This invention relates to a composition adapted ing agent which will give good fluidity and com to form moisture vaporproof coatings when appatibility are preferably employed. plied in a molten condition to a surface, such The cellulose ester which I have found to be as paper or cloth. suitable for use in compositions in accordance Compositions of various kinds have been sug- 5 with my invention are butyric acid esters of celgested for use in imparting moisture vaporproof lulose having a butyryl content of at least 42% coatings to paper, cloth, or similar material. and atotal acyl content of at least 50% and which Some of these compositions give coatings which are either fully esterified or have been hydrolyzed are soft or opaque or crease with breaking upon so that the esters have no mOre than about two impact. In other cases, the moisture vaporproofhydroxyl groups per 24 cellulose carbon atoms. ing has been not as effective as desired. In most The cellulose esters employed should have a or all of the cases known, the composition for fundamental cuprammonium-viscosity of less moisture vaporproofing has been applied by means than 10 centipoises and a viscosity within the of a solution thereof in a volatile solvent. This range of 10-100 centipoises when 1 part of ester I method involves the handling of organic solvents is dissolved in 9 parts (by weight) of acetone at and solutions, and for economical operation, the a temperature of 25 C. The fundamental cu-. collecting of the vapors thereof and recovery of prammonium viscosity is determined by obtaining the same. i in 'centipoises the viscosity of a' cuprammonium 7 One object of my invention is to provide a solution of the ester in which the cellulose of the novel composition which is of value as a non ester is ,of 2 concentration. The cellulose blocking melt-coating composition to make posesters employed should be heat stable or, in other sible the coating of surfaces without the use of a words, they should not darken or lose: viscosity volatile solvent. Another object of my invention when moderately elevated temperatures; such as is to provide a practicable melt-coating composi- 150-200 C. are applied thereto. tion which gives moisture vaporproof coatings The cellulose esters which are employed in, which are hard, firm and flexible, giving surfaces preparin my compositions may be prepared by which are clean, transparent and brilliant in reacting cellulose with butyric anhydride, prefercharacter. A further object of my invention is ably after a pretreatment using little or no acetic to provide a, cellulose ester composition which acid, the acetyl, if any, being present in such can be used for melt-coating purposes at resmall proportion in the esterification mass that stricted temperatures, such as 150-200 (3., but the prescribed proportion of butyryl is present, will be non-tacky at temperatures below 150 F. in the resulting product. The cellulose may be or 66 C. A still further object of my invention pretreated by the method described in Gardner is to provide a moisture vaporproofing coating Patent No. 2,113,301 preferably using therewith which will crease without breaking upon impact the dehydration method described in Malm Patand will heatseal, forming a strong bond. Other ent No. 2,315,973, or by the pretreatments deobjects of my invention will appear herein. scribed and claimed in Malm Patents Nos. 2,342,-

I have. found that the following composition 415 and 2,342,416, providing of course, the acetic is eminently suited for melt-coating paper, cloth acid contained is kept to a minimum. Es terifica- I or other surfaces in molten condition which upon tion of the cellulose with butyric anhydride' and cooling and solidifying gives a high moisture catalyst, such as by the methods described and vaporproofing thereto. claimed in Blanchard Patent No. 2,304,792 or Composition.-At least 40% of cellulose ester Malm Patents Nos. 2,362,576 and 2,345,406 results I containing at least 42% butyryl and at least 50% in a high butyryl cellulose ester, particularly if total acyl, 1040% di-2-ethyl hexyl phthalate, 45 the propoltion of butyryl to the total acyl is kept A7% of wax, such as paraffin, and blending sufficiently high in the esterification mass. I If agent in sufficient amount to render the wax hyd y s i mp y dfl s Preferable that it O y compatible with the plasticized cellulose ester 4 be for a sufficient time to reduce the sulfur conan to impart permanence to this composition. tent of the ester, as the substantially fully es- In order ,to obtain the best film properties, it is terified esters are the most desirable for use in desirable that the cellulose ester be present in the melt-coating processes in accordance with my maximum proportion possible or, in other words, invention. It is desirable that the esters employed the smallest proportions of'plasticizer and blendhave a char point of at least 260 C. If a high butyryl ester is available which does not have this char point, it should be stabilized, such as by the method described and claimed in Malm and Kirton Patent No. 2,250,201 or by the method described and claimed in Malm and Crane Patents Nos. 2,346,498 and 2,341,455 to a point where the ester does exhibit a char point of at least 260 C. I

The cellulose esters employed in my compositions may be either simple esters i. e. cellulose butyrates or mixed esters, i. e. cellulose acetate butyrates, cellulose propionate butyrates, cellulose acetate propionate butyrates. A small part of the butyryl in the esters may be replaced by propionyl or by fatty acid groups of 8 carbon atoms or even fatty acid groups of more than 8 carbon atoms although with the latter, the proportion should be quite small to avoid softness and stretchiness.

The plasticizer which I have found to be suitable in moisture vaporproofing melt-coating compositions in accordance with my invention is I di-Z-ethyl hexyl phthalate.

The plasticizer should be in a proportion of 10-40% of the composition. It is desirable that the least amount of plasticizer necessary to impart good fluidity to the composition be employed. With esters having a butyryl near to the tributyrate or a viscosity in the lower part of the viscosity range given, the amount of plasticizer need not be as great as with the higher viscosity cellulose esters or those with a butyryl content in the lower portion of the range given. If the plasticizer is employed in a greater proportion than that specified, the melt-coating composition, upon applying to a surface, solidifies slowly and yields a soft'non-rigid structure from which the wax has a tendency to crystallize out upon coating, giving a water vapor permeability higher than desired and also a poor appearance. A coating with a percentage ofplasticizer above that specified also exhibits a tendency to be tacky at low temperatures such as below 150 F. If plasticizer were employed in my composition in a proportion below 10%, it would be necessary to v I obtain good fluidit to employ cellulose esters of a lower viscosity than specified. The use of such low viscosity esters would result in products of undesirable physical properties, such as brittleness. The above is ofiered as a guide as to the correct proportion of plasticizer to employ in a composition in accordance with my invention for the purpose to which the composition is to be adapted. Ordinarily, the suitable proportion of di-2-ethyl hexyl phthalate will be within the l0-40% range. v

I have found parafiin to be most satisfactory as a wax for use in compositions in accordance with my invention. However, other waxes may be employed although there is some variation in their effectiveness. Beeswax and carnaubawax give good values for moisture vaporproofing in accordance with my invention, as does also ceresin and Chinese wax. Waxes generally may be employed in compositions in accordance with my invention.

The wax should be present in a proportion of at least /2% in my compositions to resist the penetration of moisture and not more than 7%, asv too great a proportion of wax tends to sepa; rate out and interfere with the brilliance and hardness of the coating" therefrom.

I have found four materials which function as blending agents and assure permanence of my compositions. The blending agents are nece s ry to cause compatability of the wax with the plasticized cellulose esters, and'to avoid separating out of the wax after the composition has been applied as a melt-coating to a surface which is to be protected. It is desirable that the blending agent be employed in the minimum proportion necessary to impart compatibility and permanence to the composition in order to allow a high proportion of cellulose ester in the composition. The materials which have been found to be particularly suitable for use as blending agents are: unhydrolyzed polyvinyl acetates having a viscosity of 1 /2-10 cps; Pentalyn A or EC which is the trade name of a pentaerythritol ester of rosin having a melting point of approximately C. and an acid number of 19 maximum; Lewisol 2L which is a rosin-maleic acid-glycerol resin having a melting range of -140 C. and an acid number of 15 maximum; and Piccolyte S-85 which is polymerized fl-pinene having a melting point of 85 C. These materials are all well known commercial products which are obtainable at the present time. The Pentalyn-type resins and their method of preparation are described in U. S. Patent No.'1,820,265 of Bent and Johnson. The Piccolyte-type resins are described in U. S. Patent No. 2,320,717 of Corkery. The proportion of blending agent used in my composition should be suflicient to render the wax compatible with the other ingredients of the composition. This depends to some extent upon the proportion of wax which is being employed. For instance, with a composition in which 1% of wax is used, a

proportion of Lewisol within the range of 23-32% will assure compatibility of the wax with the plasticized cellulose ester and permanence of the resulting composition. With the use of a largerproportion of wax, such as 5%, a larger proportion of blending agent is desirable and an amount Also, with the other blending agents, a larger proportion thereof should, be employed with an increased amount of wax. Using but a small proportion of wax, such as 1%, a proportion of Pentalyn A within the range of 5-25%' will be satisfactory, whereas with polyvinyl acetate having a viscosity of 2.5 cps. a proportion within the range of 5-20% will be most useful. In the case of Piccolyte, an amount within the range of 2-5% is sufiicient, it being desirable to employ no more than this amount in the composition. When polyvinyl acetate is employed as the blending agent, it is desirable to select the polyvinyl acetate according to viscosity to be most suitable for maximum operation. For instance, with cellulose esters in the higher part of the viscosity range specified, it is desirable to employ a polyvinyl acetate in the lower portion of the viscosity range given therefor. With, however, the lower viscosity cellulose esters, a higher viscosity polyvinyl acetate may be employed. The criterion as to the composition is that the melt of that comobtained thereby which is eminently suitable for melt-coating operations. It is desirable that the melt exhibit a viscosity between 10,000 and 50,000 centipoises for the best results in the melt-coating operation. Where the properties of the coating are important, it is desirable to have as large a proportion of cellulose ester in the composition aspossible providing the fluidity, compatibility and moistur proofing properties of the composition are sufficient. The ultimate composition desired for this purpose will vary depending upon the characteristics regarded as most important by the individual operator.

If desired, after a homogeneous melt of the ingredients of my composition is obtained, the mixture may be led directly to the coa'ting machine or it may be broken up into granules so that it may be stored and used when convenient. The granules may be melted when desired for coating in suitable heated mixing equipment or a heated piston or a worm gear extruder and fed into a melt-coating machine, particularly one which operates in a continuous manner. Various types of apparatus may be employed to coat the melt-coating composition onto the surface of a material to support the vaporproof coating. The coating may be applied onto its support by any one of four different coating methods, namely: the knife, the roll, the casting and extrusion methods. The roll-coating method involving a pick up and applicator roll seems most practical at the present time. The roll-coatingtype of machine can be adapted to a squeeze or calender method of coating by passing the cloth or paper between the two coating rolls, rotating in the direction of the material. With this method, it is possibl to coat both sides simultaneously if the melt is provided for both the top and bottom of the paper. After coating, the material may then pass through a smoothing apparatus such as depends upon the use of a heated bar of suitable design. Upon cooling, the material will be found to have a surface of good clarity and color. The various methods of applying hot melt compositions are shown. in the art and need not be repeated here. For the coating of articles which cannot be put through such apparatus, such articles aselectrical equipment, tools, packaged merchandise and the like, a coating may be applied thereto by dipping the article in the composition in a molten condition.

The following example illustrates my invention:

I Example A melt-coating composition was prepared by mixing together 6.9 pounds of a cellulose acetate butyrate containing 47% butyryl and 6% acetyl and having a viscosity of 100 centipoises in 2.10% solution in acetone, 4.5 pounds of di-Z-ethyl hexyl phthalate, 3.6 pounds of Lewisol 2L, 0.15 pound of parafiin at a temperature of 160-180 C. This mixture was stirred for 4 hours at 160-180 C. and was then coated onto a lightweight paper on a Waldron-type hot melt-coating machine. A flexible, brilliant water vaporproof paper is obtained.

Coatings of compositions in accordance with my invention have been found to give moisture vapor permeabilities at 104 F. and 80% relative humidity of .02 to .04 mg. per square centimeter per hour in coatings of a thickness of .0005 to .001 inch on glassine paper, thus comparing with the best moisture vaporproof coatings coated out from solvents.

Some typical compositions which are very suitable for melt-coating using cellulose acetate butyrate having a butyryl content of 50% and a viscosity in 10% solution in acetone of 100 centi- 6 poises, polyvinyl acetate having a viscosity of 2.5 cps. as the blending agent and 1% of paraflin wax are as follows:

Cellulose 'fg Polyvinyl ester phthalate acetate Per cent Per cent Per cent Some examples of compositions in accordance with my invention using 5% of parafl'in and Lewisol 2L as the blending agent are as follows:

' Di-2-ethyl g hexyl' Lewisol phthalate Percent Percent Percent 54 22 19 52 18 25 48 22 25 48 28 19 "Using 11% of parafiin and Lewisol 2L as the blending agent, some compositions which may be employed are as follows:

Di-2-ethyl zgi g hexyl Lewisol phthalate Percent Percent Percent 58 31 1O 52 27 20 48 21 54 10 Some typical compositions using Pentalyn as the blending agent and 1% of paraflin are as follows? Di-Z-ethyl Cellulose hex-X1 Pentalyn ester phthalate Percent Percent Percent 08 21 10 r '58 17 24 .64 19 16 27 12 Ordinarily, compositions in accordance with my invention give the most desirable coatings if the coatings are set quickly, such as by rapidly leading the coated material from the coating point to a region of lower temperature. However, I have found that even in cases where the setting takes place slowly or some opaqueness is present that the low water vapor permeability of the coating is still present.

My compositions are particularly adapted for coating sheet materials, such as cloth, paper, glassine. sheet metals or foils or the like. If desired, however, articles may be dipped in the composition in molten condition to give a moisture vaporproof coating thereon. It is preferred in the majority of cases that the paper or other material being coated be of at least moderate strength so as to avoid any danger of breakage in the coating operation. Paper or cloth coated as described herein may be employed for wrapping materials in which either loss of moisture from the contents of the package or the taking on of moisture is to be prevented. My invention is only limited by the scope of the appended claims.

I claim:

1. A non-blocking melt coating composition 7 adapted to give coatings of low moisture vapor permeability, essentially consisting of at least 40% of a heat stable butyric acid ester of cellulose, having a butyryl content of at least 42% and a total acyl content of at least 50%, a cuprammonium viscosity of less-than centipoises, a viscosity in 10% acetone solution at 25 C. of 10-200 centipoises and not more than 2 hydroxyl groups per 24 cellulose carbon atoms, sufficient di-Z-ethyl hexyl phthalate within. the range of 10-40% to impart good fluidity to the composition at 150-200 C., --'7% of wax, and suflicient of a rosin-maleic acid-glycerol resin having a melting range of 130-140 C. and an acid number of maximum to render the wax permanently compatible with the composition.

2. A non-blocking melt coating composition adapted to give coatings of low moisture vapor permeability, essentially consisting of approximately 45 parts of a heat stable cellulose acetate butyrate having a butyryl content of approximately 47%, a cuprammonium viscosity of less than 10 centipoises, a viscosity in 10% acetone solution of 25 C. of approximately 100 centipoises and not more than 2 hydroxyl groups per 24 cellulose carbon atoms, approximately 30 parts of di-Z-ethyl hexyl phthalate, approximately one part of paraflin wax, and approximately 24 parts of a rosin-maleic acid-glycerol resin having a melting point within the range of 130-140 C. and an acid number of 15 maximum.

3. A non-blocking melt-coating composition adapted to give coatings of low moisture vapor permeability, essentially consisting of at least 40% of a heat-stable butyric acid ester of cellulose having a butyryl content of at least 42% and a total acyl content of at least 50%, a cuprammonium viscosity of less than 10 centipoises, a viscosity in 10% acetone solution of 25 C. of 10-200 centipoises and not more than 2 hydroxyl groups per 24 cellulose carbon atoms, sufficient .di-2-ethyl hexyl phthalate within the range of 10-40% to impart good fluidity at 150-200 C.,

/.27% of wax, and sufficient of a blending agent to render the wax permanently compatible with the composition, said blending agent selected from the group consisting of the pentaerythritol esters of rosin having a melting point of approximately 110 C. and acid numbers of 19 maximum, and the rosin-maleic acid-glycerol resins having a melting range of l30-140 C., and acid numbers of 15 maximum.

4. A non-blocking melt-coating composition adapted to give coatings of low moisture vapor permeability, essentially consisting of at least 40% of a heat-stable butyric acid ester of cellulose having a butyryl content of at least 42% and a total acyl content of at least 50%, a cuprammonium viscosity of less than 10 centipoises, a viscosity in 10% acetone solution of 25 C. of 10-200 centipoises and not more than 2 hydroxyl groups per 24 cellulose carbon atoms, sufficient di-2-ethyl hexyl phthalate within the range of 10-40% to impart good fluidity at 150-200 C., ,/2-7% of paraflin wax, and suflicient of a blending agent to render the paraflin wax permanently compatible with the composition, said blending agent selected from the group consisting of the pentaerythritol esters of rosin having a melting point of approximately 110 C. and acid numbers of 19 maximum, and the rosin-maleic acidglycerol resins having a melting range of 130-140 C., and acid numbers of 15 maximum.

5. A non-blocking melt-coating composition adapted to give coatings of low moisture vapor permeability, essentially consisting of at least 40% of a heat-stabl cellulose acetate butyrate having a butyryl content of at least 42% and a total acyl content of at least a cuprammonium viscosity of less than 10 centipoises, a viscosity in 10% acetone solution of 25 CJof 10-200 centipoises and not more than 2 hydroxyl groups per 24 cellulose carbon atoms, suflicient di-2-ethy1 hexyl phthalate within the range of 10-40% to impart good fluidity at ISO-200 C.,

/2'7% of Wax, and sufiicient of a blending agent to render the wax permanently compatible with the composition, said blending agent selected from the group consisting of the pentaerythritol esters of rosin having a melting point of approximately 110 C. and acid numbers of 19 maximum, and the rosin-maleio acid-glycerol resins having a melting range of 130-140 C., and acid numbers of 15 maximum,

6. A non-blocking melt-coating composition adapted to give coatings of low moisture vapor permeability, essentially consisting of at least 40% of a heat-stable cellulose acetate butyrate having a butyryl content of at least 42% and a total acyl content of at least 50%, a cuprammonium viscosity of less than 10 centipoises, a viscosity in 10% acetone solution of 25 C. of 10-200 centipoises and not more than 2 hydroxyl groups per 24 cellulose carbon atoms, sufiicient di-2-ethyl hexyl phthalate within the rang of 10-40% to impart good fluidity at 150-200 C., -7% of parafiin wax, and sufiicient of a blending agent to render the paraifin Wax permanently compatible with the composition, said blending agent selected from the group consisting of the pentaerythritol esters of rosin having a melting point of approximately 110 C. and acid numbers of 19 maximum, and the rosin-maleic acid-glycerol resins having a melting range of 130-140 C., and acid numbers t of 15 maximum.

7. A non-blocking melt-coating composition adapted to giv coatings of low moisture vapor permeability, essentially consisting of at least 40% of a heat-stable butyric acid ester of cellulose having a butyryl content of at least 42% and a total acyl content of at least 50%,, a cuprammonium viscosity of less than 10 centipoises, a viscosity in 10% acetone solution of 25 C. of 10-200 centipoises and not more than 2 hydroxyl groups per 24 cellulose carbon atoms, suflicient di-2-ethyl hexyl phthalat'e within the range 'of 10-40% to impart good fluidity at 150-200" C., l -7% of parafiin Wax, and sufiicient of a pentaerythritol ester of rosin having a melting point of approximately 110 C., and an acid number of 19 maximum to render th paraffin wax permanently compatible with the composition.

8. A non-blocking melt-coating composition adapted to give coatings of low moisture vapor permeability, essentially consisting of at least 40% of -a heat-stable cellulose acetate butyrate having a butyryl content of at least 42% and a total acyl content of at least 50%, a cupram- T monium viscosity of less than 10 centipoises, a

viscosity in 10% acetone solution of 25 C. of

'10-200 centipoises and not more than 2 hydroxyl 4 groups per 24 cellulose carbon atoms, sufiicient MARTIN SALO. 

